Niyazi A.S. Al-Areqi

Influence of calcium substitution on the phase transition and ionic conductivity in BICAVOX oxide ion conductor

Samples of Bi4Ca x V2− x O11−(3 x /2)−δ in the composition range 0.07 ≤ x ≤ 0.30 were prepared by conventional solid state reactions. The stability of different phases as a function of composition was analysed by X-ray powder diffraction, FT-IR spectra, differential thermal analysis and AC impedance spectroscopy. For the compositions x ≤ 0.10, monoclinic α-phase structure is retained at room temperature. For x = 0.13, orthorhombic β-phase is observed, whereas for x ≥ 0.17, high O2−conducting tetragonal γ-phase is stabilised. However, the highest ionic conductivity σ300°C = 3.27 × 10−4 S cm−1 was observed for x = 0.17. This higher value of conductivity of the substituted compound as compared to the parent compound can be attributed to the increased oxygen ion vacancies generated as a result of cation doping. AC impedance spectroscopy reveals the fact that this ionic conductivity is mainly due to the grain contribution.

Composition dependence of polymorphism and electrical conductivity in Ce(IV)-doped Bi4V2O11

For the first time, a new member of the BIMEVOX family, namely BICEVOX, has been synthesized by the partial solid-state substitution of Ce(IV) for vanadium in parent Bi4V2O11 solid electrolyte. The electrical conductivity in Bi4Ce x V2− x O11−( x /2)− δ has been investigated in the compositional range 0 ≤ x ≤ 0.30, using FT-IR, X-ray powder diffraction, differential thermal analysis and ac impedance spectroscopy. Owing to the long-term stabilization of α- and β-polymorphs compared to other members of the BIMEVOX family, the BICEVOX system may be a prospective solid electrolyte for intermediate temperature solid oxide fuel cells due to the significantly increased conductivity at lower temperatures observed for the compositions x > 0.20.

Structural and Electrical Changes in BIMNVOX Oxide-Ion Conductor

Ceramic solid solutions Bi4MnxV2–xO11–(x/2)–δ in the composition range 0.07 ≤ x ≤ 0.30 were obtained by solid state synthesis. Structural investigations were carried out by using a combination of FT-IR and powder X-ray diffraction technique. Polymorphic transitions (β↔γ and γ′↔γ) were detected by DTA and variation in the Arrhenius plots of conductivity. The solid solutions with composition 0.07 ≤ x ≤ 0.17 are isostructural with the orthorhombic β-phase, and those with x ≤ 0.30 represent tetragonal γ-phase. With increasing Mn concentration, the conductivity of solid solutions increases from 3.684×10-6 (x = 0.07) to 2.467×10-5 (x = 0.17). AC impedance plots show that the conductivity is mainly due to the grain contribution which is evident in the enhanced short range diffusion of oxide ion vacancy in the grains with increasing temperature.

Correlation between phase structure and electrical conduction in BISNVOX system for intermediate temperature solid oxide fuel cells (IT-SOFC)

Samples of Sn4+-substituted bismuth vanadate, formulated as Bi4Sn x V2− x O11−( x /2)− δ in the composition range 0.07 ≤ x ≤ 0.30, were prepared by standard solid-state reactions. Sample characterization and the principal phase transitions (α ↔ β, β ↔ γ and γ′ ↔ γ) were investigated by FT-IR spectroscopy, X-ray powder diffraction, differential thermal analysis (DTA) and AC impedance spectroscopy. For composition x = 0.07, the α ↔ β and β ↔ γ phase transitions were observed at temperatures of 451 and 536°C, respectively. DTA thermograms and Arrhenius plots of conductivities revealed the γ′ ↔ γ phase transition at 411 and 423°C for x = 0.20 and 0.30, respectively. AC impedance plots showed that conductivity is mainly due to the grain contribution, which is evident in the enhanced short-range diffusion of oxide ion vacancy in the grains with increasing temperature. The highest ionic conductivity (5.03 × 10−5 S cm−1 at 300°C) was observed for the x = 0.17 solid solution with less pronounced thermal hysteresis.

Study on phase stabilization and electrical performance of BICO0.20−xNIxVOX solid electrolyte

BICO0.20−xNIxVOX solid electrolyte in the composition range 0 ≤ x ≤ 0.20 was synthesized by standard solid-state reactions. The influence of Ni substitution for Co on the relationship between the phase stabilization and electrical performance was investigated by means of X-ray powder diffraction (XRPD), differential thermal analysis (DTA) and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.13 whose thermal stability increases with Ni content. On the other hand, complex plane plots of impedance suggested a major contribution of polycrystalline grain interiors to the overall electrical conductivity and the fastest oxygen-vacancy diffusion in the perovskite vanadate layers at x = 0.13. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. However, a maximum ionic conductivity at lower temperatures (∼2.56 × 10−4 S cm−1 at 300 °C) was observed for the composition with x = 0.13.

Structural and electrical properties of hexavalent-substituted BIMEVOX synthesized by a microwave-assisted route

The microwave (MW)-assisted solid synthesis route was employed to prepare a new Aurivillius-type compound with the general formula Bi2Cr x V1−x O5.5+x−δ; 0≤x≤0.20 (BICRVOX). This novel synthesis method revealed that polycrystalline products of the BICRVOX system can effectively be obtained after being irradiated for 25 min rather than for the many hours of high-temperature heating needed in other conventional routes. The phase structure of MW-prepared samples was characterized by comparison with those obtained from the conventional solid-state reaction, using powder X-ray diffraction, FT-IR and differential thermal analysis techniques. Importantly, the substitution of Cr(VI) for V(V) in the parent compound resulted in stabilization of only the α - and β -phases. AC impedance spectroscopy confirmed that the MW-prepared samples possess slightly lower oxide-ion performance compared with the conventionally-prepared ones; it did, however, evidence the significant role of powerful dielectric heating of MWs in lowering the charge carrier accumulation.

Structural and cyclic volta metric investigations on BIPBVOX solid electrolyte synthesized by ethylene glycol–citric acid sol–gel route

Samples of BIPBVOX.x (Bi2V1–xPbxO5.5–x/2) in the composition range 0.05 ≤ x ≤ 0.20 were prepared by ethylene glycol– citric acid sol–gel synthesis route. Structural investigations were carried out by X–ray diffraction, DTA. The highly conducting γ′– phase was effectively stabilized at room temperature for compositions with x ≥ 0.17. Cyclic voltammetric measurements showed reversible redox reactions of vanadium and irreversible redox reaction of Bi3+ in the BIPBVOX system during the first cathodic and anodic sweep. However, a higher stability against the reduction of Bi3+ to metallic bismuth was seen for x=0.20.